A treatment system for industrial mixed waste salt containing sulfate

Abstract

The utility model discloses a treatment system for industrial mixed waste salt containing sulfate, which includes an adsorption and impurity removal unit, an acid dechlorination unit and a convection chemical unit. The industrial mixed salt is first pretreated by a pretreatment unit to remove the organic matter contained therein, and then the chlorine element is removed by acid dechlorination in the acid dechlorination unit by adding a strong acid, and finally the sulfate solution and the barium sulfide solution are prepared by convection spraying in a high-efficiency chemical reaction device of the convection chemical unit to obtain a high-purity, high-value nano-barium sulfate product and a high-purity, high-value sodium sulfide product with uniform particle size distribution, and finally the high resource utilization of industrial mixed salt is realized. The system of the utility model has the characteristics of simple structure, strong operability and low equipment investment cost, and can realize large-scale industrial application.

Description

Technical Field

[0001] The utility model relates to the treatment of industrial mixed waste salt, in particular to a treatment system of industrial mixed waste salt containing sulfate, and belongs to the technical field of industrial waste salt treatment. Background Art

[0002] Industrial waste salt is a typical industrial solid waste in the chemical, pharmaceutical, printing and dyeing industries. It has the characteristics of many types, large output, complex composition, high toxicity, high treatment cost and great environmental harm. There are two main types of waste salt treatment and utilization technologies at home and abroad, namely harmlessness and resource utilization. Waste salt harmlessness refers to the reduction or elimination of toxic and harmful components in waste salt to reduce environmental risks. Typical technologies include incineration, landfill and sea discharge. Waste salt resource utilization is the future development trend to fundamentally solve the waste salt problem. It mainly uses integrated technology to treat waste salt so that various indicators meet the reuse requirements and then it is utilized as a resource. It is mainly manifested in the resource utilization of refined salt products. Among the waste salt currently stored by enterprises, industrial mixed salt accounts for 80%. Mixed salt is difficult to dispose of and has high recycling costs. Among them, Na + , Cl - 、SO4 2- The content of sodium sulfate and sodium chloride is much higher than that of other inorganic salt ions. In the salt separation stage, the two elemental salts, sodium sulfate and sodium chloride, are mainly recovered and separated. At present, most technicians have done a lot of research on the separation technology of industrial mixed waste salt containing sodium sulfate and sodium chloride, mainly including the following: cooling or evaporation crystallization salt separation method, nanofiltration salt separation method, electrochemical salt separation method, etc.

[0003] Chinese patent CN109970079A provides a method for refining industrial waste salt, which completely decomposes and carbonizes organic matter through drying and dehydration, and secondary calcination; the crude salt after calcination is dissolved, separated, heavy metals and impurities are removed, and evaporated and crystallized to obtain refined industrial dry salt above the second level. This method is suitable for waste salt with low content of single salt or other inorganic salts such as sulfate. As shown in the scope of its applicable waste salt, the sodium chloride content is 82-96%, the water content is 2.5-7%, the organic impurities are 0.11-4%, and the sodium sulfate content is 0.4-3%. The subsequent refining processes such as barium salt method for removing sulfate and sodium sulfide method for removing heavy metals are only measures for low-content impurities, and are obviously not suitable for mixed waste salt with high sodium sulfate content; in order to facilitate the stable operation of the system and make the waste salt entering the waste salt treatment system relatively stable, the patent has a narrow limit on the components in the waste salt, which also limits the scope of application of the process.

[0004] CN 113860334A discloses a method for separating sodium sulfate and sodium chloride from industrial waste salt, comprising the following steps: S1. dissolving a certain mass of industrial waste salt with water to obtain a mixed salt solution; S2. heating the mixed salt solution obtained in step S1 to between 100°C and 115°C for distillation, filtering the precipitated salt to obtain a primary precipitated salt and a primary filtrate when the amount of water to be distilled is m1; S3. cooling the primary filtrate obtained in step S2 to 40°C to 45°C, performing reduced pressure distillation, filtering the precipitated salt to obtain a secondary precipitated salt and a secondary filtrate when the amount of water to be distilled is m2; S4. returning the secondary filtrate obtained in step S3 to the mixed salt solution in S1 for cyclic treatment; S5. detecting the content of sodium sulfate in the primary precipitated salt and the secondary precipitated salt obtained in steps S2 and S3. In this method, a large amount of calculations are required for each distillation, and the end point of the distillation is difficult to control, and the quality of the obtained product is unstable.

[0005] CN113772692A discloses a method for treating and recycling waste salt, wherein the method dissolves the crushed waste salt to obtain high-salt wastewater; adjusts the pH to 4-5, purifies the high-salt wastewater through an adsorption system, separates and removes impurities, and then adjusts the pH to neutral, performs nanofiltration salt separation and evaporation crystallization. The operation procedure is complicated, the process is long, and high requirements are placed on the nanofiltration membrane.

[0006] At present, most technologies can separate sodium sulfate and sodium chloride from waste salt, but the salt separation process is difficult, hard to control, and costly. In addition, the products obtained are sodium chloride and sodium sulfate, both of which are low-value products. The investment is far greater than the return, and the product market is highly saturated, supply exceeds demand, and sales are difficult. The high-value conversion and utilization of industrial waste salt has not been achieved, and resource utilization has not been truly realized. Utility Model Content

[0007] Aiming at the problem that the existing industrial mixed salt treatment means in the prior art are single, the treatment process is long, the treatment cost is high, and the added value of the recovered products is low, and the high-value resource utilization of industrial mixed salt is not truly realized, the utility model provides a treatment system for industrial mixed waste salt containing sulfate and a treatment process for industrial mixed waste salt using the system, pre-treating the industrial mixed salt by a pre-treatment unit to remove the organic matter contained therein, and the mixed salt solution after the organic matter is removed is acid-dechlorinated by adding a strong acid in an acid dechlorination unit to remove the chlorine element therein (and recycled to make hydrochloric acid), and further obtain a high-concentration sulfate solution, and finally the sulfate solution and the high-purity barium sulfide solution prepared from the waste barium material are prepared in a high-efficiency chemical reaction device by convection spraying to obtain a high-purity, uniformly distributed high-value nano barium sulfate product and a high-purity, high-value sodium sulfide product, and finally realize the high resource utilization of industrial mixed salt. In addition, the waste gas and waste liquid generated during the use of the system can be internally digested, and zero discharge of waste gas and waste liquid is achieved. The system of the utility model has the characteristics of simple structure, strong operability and low equipment investment cost, and can realize large-scale industrial application.

[0008] In order to achieve the above-mentioned purpose, the technical solution adopted by the utility model is specifically described as follows:

[0009] According to a first embodiment of the present invention, a system for treating industrial mixed waste salt containing sulfate is provided:

[0010] A treatment system for industrial mixed waste salt containing sulfate, the system comprises an adsorption impurity removal unit, an acid dechlorination unit and a convection chemical combination unit. The adsorption impurity removal unit comprises a washing and filtering device and an activated carbon adsorption device which are sequentially arranged in series. The acid dechlorination unit comprises an acidolysis device, a freezing separation device and a dissolution tank. The convection chemical combination unit comprises a high-efficiency chemical combination barrel and an upper annular spraying pipe and a lower annular spraying pipe which are arranged in parallel in the high-efficiency chemical combination barrel, an upper annular spraying pipe is provided with an upper annular nozzle, and a lower annular spraying pipe is provided with a lower annular nozzle, and an upper spray hole of the upper annular nozzle is arranged opposite to a lower spray hole of the lower annular nozzle. The discharge end of the mixed waste salt conveying device is connected to the feed port of the washing and filtering device, the discharge port of the washing and filtering device is connected to the inlet of the activated carbon adsorption device through an infusion pipe, the discharge port of the activated carbon adsorption device is connected to the inlet of the acidolysis device through an infusion pipe, the discharge port of the acidolysis device is connected to the inlet of the freezing separation device through an infusion pipe, the discharge port of the freezing separation device is connected to the feed port of the dissolution tank through the infusion pipe, the discharge port of the dissolution tank is connected to the inlet of the lower annular spraying pipe through the infusion pipe, and the inlet of the upper annular spraying pipe is connected to the barium sulfide solution conveying pipe.

[0011] Preferably, the system also includes a pretreatment unit, which is a pyrolysis furnace or an incinerator, the discharge end of the mixed waste salt conveying device is connected to the feed port of the pyrolysis furnace or the incinerator, and the discharge port of the pyrolysis furnace or the incinerator is connected to the feed port of the washing and filtering device through a conveying pipe.

[0012] Preferably, the washing and filtering device is further provided with a water inlet connected to a water inlet pipe. A screen is further provided inside the washing and filtering device, and a liquid discharge port of the washing and filtering device is located below the screen.

[0013] Preferably, the acidolysis device comprises an acidolysis reaction tank and a first waste gas absorption tank. The liquid inlet of the acidolysis reaction tank is connected to the liquid discharge port of the activated carbon adsorption device through a liquid infusion pipe, and the exhaust port of the acidolysis reaction tank is connected to the air inlet of the first waste gas absorption tank through an air infusion pipe. The acidolysis reaction tank is also provided with an acid addition port, and the acidolysis reaction tank is also provided with a first heating mechanism and a first temperature detector. The first heating mechanism is one of a heating tube, a heating plate, and a heating wire.

[0014] Preferably, the liquid discharge port of the freezing separation device is also connected to the acid addition port of the acidolysis reaction tank through an acid liquid circulation pipeline.

[0015] Preferably, the high-efficiency chemical combination barrel comprises a barrel body, a first stirring motor, a first stirring shaft and a first stirring blade. The first stirring motor is arranged on the top of the barrel body, the upper end of the first stirring shaft is connected to the first stirring motor, and the lower end thereof extends into the barrel body, and the first stirring blade is arranged in the middle and lower part of the first stirring shaft. The first stirring blade is a sheet-like structure whose thickness gradually decreases along its rotation direction and whose upper surface is an inclined surface. A second temperature detector is also arranged in the barrel body.

[0016] Preferably, the upper annular spraying pipe and the lower annular spraying pipe are both fixed inside the barrel body by a fixing bracket and are both located above the stirring blades, and the stirring shaft passes through the ring centers of the upper annular spraying pipe and the lower annular spraying pipe in sequence. The upper annular spraying pipe is evenly distributed along its circumference with a plurality of upper annular nozzles facing vertically downward, and the lower annular spraying pipe is evenly distributed along its circumference with a plurality of lower annular nozzles facing vertically upward, and the number of the upper annular nozzles is consistent with the number of the lower annular nozzles, and corresponds one to one.

[0017] Preferably, the upper ring nozzle includes an upper injection hole, a herringbone nozzle and an ultrasonic block. The herringbone nozzle is composed of an upper through pipe, a herringbone pipe and a lower through pipe connected in series from top to bottom. The upper through pipe of the herringbone nozzle is connected to the upper annular spraying pipeline, the upper injection hole is provided on the inner wall of the lower through pipe of the herringbone nozzle, and the ultrasonic block is arranged on the outer wall of the lower through pipe of the herringbone nozzle. Preferably, the upper ring nozzle includes a plurality of herringbone pipes, and the plurality of herringbone pipes are evenly arranged around the lower side of the upper through pipe, and the upper ends of all the herringbone pipes are simultaneously connected to the lower end of the upper through pipe, and the lower end of each herringbone pipe is connected to the lower through pipe.

[0018] Preferably, the lower annular nozzle includes a lower injection hole, a vertical nozzle and a movable tube. The lower end of the vertical nozzle is connected to the lower annular spray pipe, and the movable tube is sleeved from top to bottom in the tube cavity of the vertical nozzle, and can move up and down in the tube cavity of the vertical nozzle. The lower injection hole is arranged on the tube wall of the movable tube. The outer diameter of the movable tube is smaller than the inner diameter of the vertical nozzle, and an annular baffle is arranged around the outer side of the bottom end of the movable tube, and the top of the vertical nozzle is a constricted design. The upper end of the vertical nozzle is flush with the lower end of the herringbone nozzle lower through pipe, and the top of the movable tube is provided with a herringbone limiting protrusion matching the herringbone nozzle. Preferably, when the movable tube is fully extended out of the vertical nozzle, the upper injection hole is opposite to the lower injection hole one by one, and in the vertical direction, the distance between the upper injection hole and the lower injection hole at the same horizontal height gradually increases from top to bottom.

[0019] Preferably, the system further comprises a purification and refinement unit, the purification and refinement unit comprising a stirring barrel and a cylindrical screen, the stirring barrel comprising a cylindrical barrel body and a conical barrel bottom arranged at the lower end of the barrel body. The cylindrical screen is fixed inside the barrel body of the stirring barrel by a fixed bracket, and sieve holes are provided on the top wall, bottom wall and side wall of the cylindrical screen. A second stirring motor is arranged on the top of the stirring barrel, the upper end of the second stirring shaft is connected to the second stirring motor, and the lower end thereof passes through the cylindrical screen downward and extends to the inner cavity of the stirring barrel located below the cylindrical screen. A second stirring blade is arranged on the second stirring shaft located inside the cylindrical screen and below the cylindrical screen. A liquid injection pipe and a feed pipe are also arranged on the top of the stirring barrel, and the lower end of the feed pipe extends downward to the inside of the cylindrical screen, and the upper end of the feed pipe is connected to the salt outlet of the high-efficiency chemical combination barrel through a coarse material conveying device.

[0020] Preferably, the system further comprises an evaporation concentration device and a second waste gas absorption tank, the liquid inlet of the evaporation concentration device is connected to the liquid discharge port of the high-efficiency combination barrel through a liquid infusion pipe, the gas inlet of the second waste gas absorption tank is connected to the gas outlet of the high-efficiency combination barrel through a gas infusion pipe, and the liquid discharge port of the second waste gas absorption tank is connected to the liquid inlet of the evaporation concentration device through a liquid infusion pipe. The second waste gas absorption tank is provided with an alkali solution inlet.

[0021] Preferably, a third temperature detector is provided in the barrel of the mixing barrel. An ultrasonic generating plate and a second heating mechanism are provided on the conical barrel bottom of the mixing barrel, and the second heating mechanism is one of a heating tube, a heating plate and a heating wire.

[0022] Preferably, the pore size of the sieve is 10-200 nm, preferably 30-180 nm, more preferably 50-150 nm.

[0023] Preferably, the second stirring blade is an arc-shaped stirring blade, and a serrated protrusion is also provided on the blade edge in the rotation direction thereof.

[0024] According to a second embodiment of the present invention, a process for treating industrial mixed waste salt containing sulfate using a system for treating industrial mixed waste salt containing sulfate is provided, and the process comprises the following steps:

[0025] 1) Mixed salt pretreatment: According to the content of organic matter in the industrial mixed waste salt, the industrial mixed waste salt is divided into low organic mixed waste salt and high organic mixed waste salt. The low organic mixed waste salt is directly subjected to step 2). The high organic mixed waste salt is heat-treated to be converted into low organic mixed waste salt and then subjected to step 2).

[0026] 2) Activated carbon adsorption and impurity removal: The low organic mixed waste salt obtained in step 1) is washed with water, and then activated carbon is added to the waste salt solution after washing for adsorption treatment. After the adsorption is completed, solid-liquid separation is performed to obtain a refined salt solution and waste activated carbon. The refined salt solution is directly subjected to step 3), and the waste activated carbon is regenerated and recycled for adsorption treatment of the salt solution after washing.

[0027] 3) Acid dechlorination: add sulfuric acid solution to the refined salt solution, heat and react, and use water or dilute hydrochloric acid to recover HCl produced during the reaction to obtain hydrochloric acid. After the reaction is completed, cool the reaction liquid for crystallization, and obtain sodium bisulfate crystals and crystallized liquid after solid-liquid separation. The crystallized liquid is mixed with concentrated sulfuric acid and recycled for step 3).

[0028] 4) Convection combination: firstly, the sodium bisulfate crystals obtained in step 3) are made into a sodium bisulfate solution, and then the sodium bisulfate solution and the barium sulfide solution are mixed and reacted in a high-efficiency chemical combination reaction device in a convection jet manner. After the reaction is completed, solid-liquid separation is performed to obtain a coarse nano-scale barium sulfate precipitate and a sodium sulfide solution. The sodium sulfide solution is concentrated and crystallized to obtain sodium sulfide crystals.

[0029] Preferably, the process further comprises the following steps:

[0030] 5) Refining treatment: The crude nano-scale barium sulfate precipitate is washed with water and dilute sulfuric acid in the purification and refinement device, and redispersed under the dual action of ultrasound and stirring mechanism. After solid-liquid separation, high-purity nano-scale barium sulfate is obtained, and the separated waste water and waste acid are recycled for water washing and acid washing respectively. And / or

[0031] 6) Waste gas treatment: In step 4), the hydrogen sulfide gas released during the reaction is absorbed by alkaline solution to obtain a sodium sulfide-rich absorption liquid, and the sodium sulfide-rich absorption liquid is mixed with a sodium sulfide solution and then concentrated and crystallized.

[0032] Preferably, in step 1), the industrial mixed waste salt is a mixed salt containing sodium sulfate and sodium chloride. The mass content of sodium sulfate is not less than 20%, preferably not less than 30%, and more preferably not less than 40%. The total mass content of sodium sulfate and sodium chloride is not less than 70%, preferably not less than 80%, and more preferably not less than 90%.

[0033] Preferably, in step 1), industrial mixed waste salt with an organic matter mass content not higher than 12% (preferably not higher than 10%, more preferably not higher than 8%, and even more preferably not higher than 5%) is called low-organic mixed waste salt, otherwise it is called organic mixed waste salt.

[0034] and / or

[0035] Preferably, in step 1), the heat treatment is specifically: treating the high-organic mixed waste salt at a temperature of 100-800° C. for 1-8 h, preferably at a temperature of 200-700° C. for 1.5-6 h.

[0036] Preferably, in step 2), the amount of water used for washing is 2-5 times, preferably 2.5-4 times, the mass of the low organic mixed waste salt.

[0037] Preferably, in step 2), the adsorption treatment time is not less than 10 minutes, preferably 1-3 hours.

[0038] Preferably, in step 3), the sulfuric acid solution is concentrated sulfuric acid with a mass fraction of 50-98%, preferably 60-90%. The amount of the sulfuric acid solution is such that the molar ratio of sulfuric acid to sodium chloride is 1-5:1, preferably 1-3:1.

[0039] Preferably, in step 3), the heating reaction is specifically heating to 60-100° C. and reacting for 0.5-4 h, preferably heating to 70-90° C. and reacting for 1-3 h.

[0040] Preferably, in step 4), the concentration of the barium sulfide solution is 0.5-1.5 mol / L. The amount of the barium sulfide solution is such that the molar ratio of barium sulfide to sodium bisulfate is 1-2:1, preferably 1-1.5:1, and more preferably 1-1.3:1.

[0041] Preferably, the barium sulfide solution is a leaching solution after the waste barium material is washed with water. The mass content of barium sulfide in the waste barium material is not less than 5%, preferably not less than 8%, and more preferably not less than 10%.

[0042] In the prior art, the resource disposal of industrial mixed waste salt with high sodium sulfate and sodium chloride content generally adopts the traditional idea of ​​how to separate sodium sulfate and sodium chloride and recycle them to obtain sodium sulfate and sodium chloride products respectively. Most technicians have done a lot of research on the separation technology of industrial mixed waste salt containing sodium sulfate and sodium chloride. There should be the following There are three types of salt separation methods: cooling or evaporation crystallization salt separation method, nanofiltration salt separation method, electrochemical salt separation method, etc. These technologies can separate sodium sulfate and sodium chloride from waste salt, but the products obtained after salt separation are only sodium chloride and sodium sulfate. The cost of salt separation and salt recovery is high, and sodium chloride and sodium sulfate are both low-value products. The market is highly saturated, supply exceeds demand, and they cannot be sold. They have not achieved high-value conversion and utilization of industrial waste salt, and have not achieved resource utilization in a real sense.

[0043] In the utility model, in view of the problems of the prior art that the industrial mixed salt treatment means are single, the treatment process is long, the treatment cost is high, and the added value of the recovered products is low, the utility model pre-treats the industrial mixed waste salt containing sodium chloride and sodium sulfate by heat treatment and activated carbon adsorption to remove the organic and inorganic impurities contained therein, until the organic and inorganic impurities in the waste salt are completely removed to avoid affecting the subsequent process, wherein the activated carbon adsorbed with impurities can be recycled. Then, sulfuric acid with a concentration of more than 50% is used to react with the pre-treated refined salt solution (control the temperature at 60-100°C for 0.5-4h), and the volatilized hydrogen chloride gas is collected to obtain dilute hydrochloric acid. After the chloride ions in the solution are completely converted, the reacted solution is cooled to room temperature to obtain sodium bisulfate crystals, and the liquid after crystallization can be recycled for thermal reaction with the pre-treated mixed waste salt. After washing, impurity removal and refining, the sodium bisulfate crystals are obtained to obtain a high-purity and high-value sodium bisulfate product. Further, sodium bisulfate can be made into a solution and in proportion with a high-purity barium sulfide solution prepared from waste barium material in an efficient chemical reaction reactor by means of a convection jet chemical reaction to obtain a crude nanometer barium sulfate and sodium sulfide solution, the generated hydrogen sulfide gas is absorbed by sodium hydroxide, and after saturation, it is evaporated and concentrated together with a dilute sodium sulfide solution to obtain a high-purity sodium sulfide product, while the crude nanometer barium sulfate is purified and refined to obtain a high-purity nanometer-scale barium sulfate product with a narrow particle size distribution. In other words, the utility model does not need to carry out salt separation treatment on sodium sulfate and sodium chloride, and only by removing organic matter and recovering chlorine, low-value sodium chloride and sodium sulfate can be converted into high-value high-purity sodium bisulfate. This process does not require high-temperature conversion, does not require the addition of a salting agent, and does not require the separation of sodium sulfate and sodium chloride, which solves the problem of the difficulty of separating sodium sulfate and sodium chloride. Further, sodium bisulfate can also be used as a raw material to carry out efficient chemical combination with waste barium material to prepare nanometer barium sulfate products and sodium sulfide products with higher value and greater market demand. In a true sense, the resource recovery of industrial mixed waste salt and waste barium material is realized.

[0044] In the utility model, the industrial mixed waste salt is a sodium sulfate and sodium chloride system, wherein the mass content of sodium sulfate is not less than 20% (preferably not less than 30%, more preferably not less than 40%), and the total mass content of sodium sulfate and sodium chloride is not less than 70% (preferably not less than 80%, more preferably not less than 90%). The heat treatment in the pretreatment is generally treated at a temperature of 100-800°C for 1-8h (preferably at a temperature of 200-700°C for 1.5-6h) to remove most of the organic impurities. The heat treatment can adopt conventional high-temperature pretreatment methods, such as high-temperature pyrolysis carbonization, incineration, activated carbon adsorption, etc.

[0045] In the utility model, the convective jet chemical reaction of the sodium bisulfate solution and the barium sulfide solution is specifically to spray the sodium bisulfate solution and the barium sulfide solution respectively through nozzles arranged opposite to each other, and to carry out efficient reaction through the mutual collision and mixing of high-speed fine jets, so that the two raw materials are fully contacted, the raw materials are evenly mixed, and the reaction is ensured to be thorough, and problems such as uneven mixing of raw materials, excessive local concentration, incomplete reaction, and agglomeration of reaction products resulting in coarse particle size and uneven distribution are avoided.

[0046] In the utility model, the combination of sodium bisulfate solution and barium sulfide solution is carried out in a self-made high-efficiency combination reaction device. Center The high-efficiency chemical reaction device provided by the utility model is specifically to set an upper annular spraying pipe and a lower annular spraying pipe with the same annular center and parallel to each other in the inner cavity of the high-efficiency chemical barrel. The upper annular spraying pipe and the lower annular spraying pipe respectively realize the feeding of sodium bisulfate solution and barium sulfide solution through different feeding pipes and feeding pumps, and are used to feed the high-efficiency chemical barrel simultaneously. The two materials entering the upper annular spraying pipe and the lower annular spraying pipe are respectively sprayed out simultaneously through the upper annular nozzle and the lower annular nozzle which are vertically and evenly spaced and relatively distributed above their respective annular tubes. The high-speed jet of raw material sprayed from the upper annular nozzle collides with the high-speed jet of another raw material sprayed from the lower annular nozzle, so that the two raw materials are fully contacted and a uniform mixing reaction of the raw materials is realized. That is, the high-efficiency chemical reaction device of the utility model realizes the high-efficiency reaction of barium sulfide and sodium bisulfate by setting a high-efficiency convection injection device, solves the problems of local supersaturation, uneven reaction, incomplete reaction, etc., and prepares high-value nano-level barium sulfate.

[0047] In the utility model, the upper ring nozzle is a trumpet-shaped structure with a double herringbone cross section, and a material channel is formed between the double herringbone shell layers. It specifically includes an upper injection hole, at least one herringbone nozzle and an ultrasonic block. The herringbone nozzle is composed of an upper through pipe, a herringbone pipe and a lower through pipe connected in series from top to bottom. The upper through pipe of the herringbone nozzle is connected to the upper annular spraying pipeline, and the upper injection hole is arranged on the inner side wall of the lower through pipe of the herringbone nozzle. The barium sulfide solution in the upper annular spraying pipeline flows through the upper through pipe, the herringbone pipe and the lower through pipe in sequence, and then sprays out from the upper injection hole located on the inner side of the lower through pipe to react efficiently with the sodium bisulfate solution. An ultrasonic block is also arranged on the outer side wall of the lower through pipe of the herringbone nozzle, that is, the ultrasonic block and the upper injection hole are arranged horizontally relative to each other, and the ultrasonic emission direction is consistent with the flow direction of the barium sulfide solution. Through the arrangement of the ultrasonic block, on the one hand, the uniformity of the barium sulfide solution can be improved, and on the other hand, the clogging of the upper injection hole can be avoided. Furthermore, the upper ring nozzle includes a plurality of herringbone tubes, which are evenly arranged around the lower part of the upper through tube, and the upper ends of all the herringbone tubes are simultaneously connected to the lower end of the upper through tube, and the lower end of each herringbone tube is connected to the lower through tube. It should be noted that the plurality of herringbone tubes may not be connected to each other in the circumferential direction to form a plurality of small material channels, or may be connected to each other to form a large material channel.

[0048] In the utility model, the lower ring nozzle is arranged opposite to the upper ring nozzle, and includes a lower injection hole, a vertical nozzle and a movable tube. The lower end of the vertical nozzle is connected to the lower annular spray pipe, the movable tube is sleeved from top to bottom in the tube cavity of the vertical nozzle, and can move up and down in the tube cavity of the vertical nozzle, and the lower injection hole is arranged on the tube wall of the movable tube. The outer diameter of the movable tube is smaller than the inner diameter of the vertical nozzle, and an annular baffle is arranged around the outer side of the bottom end of the movable tube, and the top of the vertical nozzle is a constricted design. The upper end of the vertical nozzle is flush with the lower end of the herringbone nozzle lower through pipe, and the top of the movable tube is provided with a herringbone limiting protrusion matching the herringbone nozzle. The sodium bisulfate solution in the lower annular spray pipe enters the vertical spray pipe, and pushes the movable pipe to extend upward through the annular baffle. Under the dual action of the annular baffle and the herringbone limit protrusion, when the movable pipe is fully extended from the vertical spray pipe, the upper spray hole and the lower spray hole are opposite to each other, and the distance between the upper spray hole and the lower spray hole at the same horizontal height gradually increases from top to bottom, that is, the upper annular nozzle forms an annular surround on the lower annular nozzle. The arrangement of the upper spray hole and the lower spray hole opposite to each other makes the barium sulfide solution sprayed from the upper spray hole and the sodium bisulfate solution sprayed from the lower spray hole form a collision flow, which is quickly dispersed and reacted to generate barium sulfate precipitation. The arrangement of the distance between the upper spray hole and the lower spray hole gradually increasing from top to bottom provides sufficient space for the reaction of barium sulfide and sodium bisulfate, and also provides sufficient space for the falling of barium sulfate precipitation, so as to prevent the generated nano barium sulfate crystals from agglomerating and growing with each other.

[0049] In the utility model, the upper ring nozzle of the barium sulfide solution and the lower ring nozzle of the sodium bisulfate solution are arranged relative to each other in an up-down direction, which is conducive to showing the advantages of the herringbone nozzle design. The design of the herringbone injection device, on the one hand, effectively prevents the nano-scale barium sulfate generated by the convection collision of the barium sulfide solution and the sodium bisulfate solution from entering the injection device and depositing, and also creates a convection collision reaction space for the barium sulfide solution and the sodium bisulfate solution, avoiding the interference of the slurry. On the other hand, driven by the pressure of the sodium bisulfate solution, the circular injection hole on the sodium bisulfate solution injection device moves upward (the movable tube moves upward as a whole), which makes it fit well with the upper ring nozzle that fixes the injection of the barium sulfide solution, and at the same time prevents the circular injection holes (upper injection hole and lower injection hole) from being blocked by the slurry, and also effectively avoids the slurry backflow and affects the purity of the raw materials.

[0050] In the utility model, heating blocks (first heating mechanism) are evenly laid in the outermost ring area at the bottom of the high-efficiency chemical combination barrel, and the temperature is automatically controlled by the temperature control system to promote uniform heating of the solution. At the same time, it also effectively prevents the barium sulfide solution and the sodium bisulfate solution from cooling and precipitating crystals due to the room temperature being lower than the crystallization point, thereby blocking the upper annular spraying pipe, the lower annular spraying pipe and the circular spraying hole.

[0051] In the utility model, the stirring blade (first stirring blade) in the high-efficiency chemical combination barrel is a sheet-like structure whose thickness gradually decreases along its rotation direction and whose upper surface is an inclined surface. The edge of the blade is polished to make the edge sharp. When stirring the slurry, it can effectively promote the uniform mixing of the slurry and avoid the formation of local oversaturation, and can also perform a certain cutting effect on the nano-level barium sulfate and reduce the distribution range of the nano-level barium sulfate particle size.

[0052] In the utility model, the nano-barium sulfate generated in the high-efficiency chemical combination barrel will also carry a certain amount of impurities, and there is a certain degree of secondary agglomeration, which greatly reduces the product value of the barium sulfate. Therefore, in order to simultaneously ensure the purity of the nano-barium sulfate and completely prevent the agglomeration phenomenon, the utility model abandons the traditional method of adding a dispersant during the reaction process (adding a dispersant will introduce new impurities and reduce the purity of the product), and further adds a post-purification and refinement unit for nano-barium sulfate after the high-efficiency chemical combination device. The purification and refinement unit includes a stirring barrel and a cylindrical screen. The stirring barrel is a closed cylindrical structure, and the cylindrical screen (a fully closed cylindrical structure with sieve holes) is coaxial. The sleeve is arranged inside the mixing barrel, and sieve holes are provided on the side wall and bottom wall of the cylindrical screen. The nano-barium sulfate deposited in the high-efficiency chemical combination barrel is directly transported to the inside of the cylindrical screen through the feed pipeline, and then water is introduced in turn for washing to remove the sodium sulfide carried by it, and then a small amount of other insoluble impurities are removed by acid washing, and the nano-barium sulfate that has been agglomerated is further refined and screened under the dual effects of stirring and ultrasound to break up the agglomerated nano-barium sulfate. The purification and refinement unit integrates multiple functions such as washing, washing, acidification, purification, refinement, and screening, which can further improve the purity, fineness, whiteness, viscosity and other indicators of nano-barium sulfate, and effectively guarantee the product value of nano-barium sulfate.

[0053] In the utility model, after the nanometer barium sulfate prepared by the efficient chemical reaction is filtered, although the particle size of the barium sulfate has reached the nanometer level, the barium sulfate contains sodium sulfide and the barium sulfate has high viscosity and is easy to agglomerate, which will occur again during the neutralization and washing process. Agglomeration leads to unclean product washing, low purity and increased particle size. Cutting The stirring paddle (to solve the problem of high viscosity of barium sulfate and difficulty in dispersion) and the nano-dispersion screening device (the cylindrical screen is set in a cage shape to screen out the products with the required particle size and continue to disperse those that do not meet the requirements) can achieve the purification and refinement of nano-barium sulfate and produce nano-scale barium sulfate with stable and controllable particle size. This can ensure that the particle size of the generated nano-scale barium sulfate is stable and controllable.

[0054] In the utility model, the function of the high-efficiency chemical combination barrel in the utility model is to convert the sodium sulfide solution leached from the waste barium material and the sodium bisulfate solution into nano-scale barium sulfate precipitation and sodium sulfide solution, and the function of the purification and refinement unit is to solve the problems of purity, fineness, whiteness, viscosity, etc. of nano-scale barium sulfate, especially purity. Only when the nano-scale barium sulfate is dispersed, the smaller the particle size, the less impurities it contains, the purer the nano-scale barium sulfate obtained, and the higher the added value of its product. The high-efficiency chemical combination and the purification and refinement process are two indispensable links in the preparation of nano-scale barium sulfate, and neither of them can be missing. Only when the barium sulfate obtained by the high-efficiency chemical combination process is nano-scale, can it be redispersed, washed and converted into a nano-scale barium sulfate product with uniform particle size distribution through sieve holes through ultrasound and stirring. At the same time, only through the subsequent purification and refinement process can the nano-scale barium sulfate obtained by the high-efficiency chemical combination process be prevented from agglomerating and the purity and whiteness of the nano-scale barium sulfate be improved.

[0055] In the utility model, the utility model provides a series of scientific and reasonable chemical process technology methods to convert industrial mixed waste salt containing sodium sulfate and sodium chloride into high-value products such as sodium bisulfate, nano-level barium sulfate, sodium sulfide, etc., thereby truly realizing the resource utilization of waste salt.

[0056] In the utility model, the barrel diameter of the high-efficiency chemical combination barrel is 0.1-100m, preferably 0.3-80m, more preferably 0.5-50m, and its height is 0.1-80m, preferably 0.2-60m, more preferably 0.3-40m. The diameters of the upper annular spraying pipe and the lower annular spraying pipe are independently 0.1-50cm, preferably 0.2-30cm, more preferably 0.3-20cm.

[0057] Compared with the prior art, the beneficial technical effects of the utility model are as follows:

[0058] 1: The utility model innovatively provides a treatment system for industrial mixed waste salt containing sulfate. The system does not need to separate sodium sulfate and sodium chloride in the industrial mixed waste salt. The system directly removes organic matter through the heat treatment mechanism and activated carbon adsorption mechanism in the pretreatment unit, and removes and recovers chlorine elements through the acid dechlorination unit to prepare a sodium bisulfate product with higher economic value. It has the advantages of low treatment cost and high added value of the recovered products.

[0059] 2: The utility model uses a specially designed high-efficiency chemical reaction device to simply and quickly prepare higher-value nano-scale barium sulfate and sodium sulfide by convection jet chemical combination of sodium bisulfate and barium sulfide recovered from waste barium slag. At the same time, a specially designed purification and refinement device is used to effectively ensure the particle size stability and purity of nano-scale barium sulfate, further improving the economic value of nano-scale barium sulfate.

[0060] 3: The waste gas and waste liquid generated during the use of the treatment system described in the utility model can be internally digested, achieving zero emission of waste gas and waste liquid, with strong operability and low equipment investment cost, and can be applied in large-scale industrialization.

[0061] 4: The processing system provided by the utility model has the characteristics of simple structure, low cost, no secondary pollution, easy operation, high production efficiency, high product added value, etc. It has broad market prospects and significant economic benefits. BRIEF DESCRIPTION OF THE DRAWINGS

[0062] Figure 1 It is an overall simplified diagram of the processing system described in the utility model.

[0063] Figure 2 It is a schematic diagram of the overall structure of the high-efficiency chemical combination barrel of the utility model.

[0064] Figure 3 It is a schematic diagram of the upper ring nozzle and the lower ring nozzle of the utility model in the relatively open (left) and closed (right) states.

[0065] Figure 4 It is an enlarged schematic diagram of the utility model when the upper injection hole corresponds to the lower injection hole.

[0066] Figure 5 It is a schematic diagram of the structure of the purification and refinement unit of the utility model.

[0067] Figure 6 It is a structural schematic diagram of a utility model cylindrical screen.

[0068] Figure 7 This is a schematic diagram of the structure of the second stirring blade of the utility model.

[0069] Figure numerals: 1: washing and filtering device; 101: mixed waste salt conveying device; 102: water inlet pipeline; 103: screen; 2: activated carbon adsorption device; 3: acid hydrolysis device; 301: acid hydrolysis reaction tank; 302: first waste gas absorption tank; 303: acid addition port; 304: first heating mechanism; 305: first temperature detector; 4: freezing and separation device; 401: acid liquid circulation pipeline; 5: dissolution tank; 6: high-efficiency chemical combination barrel; 601: barrel body; 602: first stirring motor; 603: first stirring shaft; 604: first stirring blade; 605: second temperature detector; 606: fixed bracket; 7: upper annular spraying pipeline; 701: upper annular nozzle; 7011: upper injection hole; 7012: herringbone nozzle; 701 3: ultrasonic block; 8: lower annular spraying pipe; 801: lower annular nozzle; 8011: lower injection hole; 8012: vertical nozzle; 8013: movable pipe; 8014: annular baffle; 8015: herringbone limit protrusion; 9: barium sulfide solution delivery pipeline; 10: pyrolysis furnace or incinerator; 11: stirring barrel; 1101: second stirring motor; 1102: second stirring shaft; 1103: second stirring blade; 1104: injection pipe; 1105: feeding pipe; 1106: third temperature detector; 1107: ultrasonic generating plate; 1108: second heating mechanism; 12: cylindrical screen; 1201: fixed rod; 1202: sieve hole; 13: coarse material conveying device; 14: evaporation concentration device; 15: second exhaust gas absorption tank. DETAILED DESCRIPTION

[0070] The technical solution of the utility model is illustrated below, and the scope of protection requested for the utility model includes but is not limited to the following embodiments.

[0071] A system for treating industrial mixed waste salt containing sulfate, the system comprises an adsorption and impurity removal unit, an acid dechlorination unit and a convection chemical combination unit. The adsorption and impurity removal unit comprises a washing and filtering device 1 and an activated carbon adsorption device 2 which are sequentially arranged in series. The acid dechlorination unit comprises an acidolysis device 3, a freezing separation device 4 and a dissolution tank 5. The convection chemical combination unit comprises a high-efficiency chemical combination barrel 6 and an upper annular spraying pipe 7 and a lower annular spraying pipe 8 which are arranged in parallel up and down in the high-efficiency chemical combination barrel 6. An upper annular nozzle 701 is arranged on the upper annular spraying pipe 7, and a lower annular nozzle 801 is arranged on the lower annular spraying pipe 8. The upper spray hole 7011 of the upper annular nozzle 701 is arranged opposite to the lower spray hole 8011 of the lower annular nozzle 801. The discharge end of the mixed waste salt conveying device 101 is connected to the feed port of the washing and filtering device 1, and the discharge port of the washing and filtering device 1 is connected to the activated carbon adsorption device 2 through an infusion pipe. The liquid inlet of the activated carbon adsorption device 2 is connected to the acid hydrolysis device 3 through the infusion tube. ProgressThe liquid inlet of the acidolysis device 3 is connected to the liquid inlet of the freezing separation device 4 through a liquid infusion pipe, the discharge port of the freezing separation device 4 is connected to the feed port of the dissolution tank 5 through a liquid infusion pipe, the discharge port of the dissolution tank 5 is connected to the liquid inlet of the lower annular spraying pipe 8 through a liquid infusion pipe, and the liquid inlet of the upper annular spraying pipe 7 is connected to the barium sulfide solution delivery pipe 9.

[0072] Preferably, the system also includes a pretreatment unit, which is a pyrolysis furnace or an incinerator 10, and the discharge end of the mixed waste salt conveying device 101 is connected to the feed port of the pyrolysis furnace or the incinerator 10, and the discharge port of the pyrolysis furnace or the incinerator 10 is connected to the feed port of the washing and filtering device 1 through a conveying pipe.

[0073] Preferably, the washing and filtering device 1 is further provided with a water inlet connected to the water inlet pipe 102. A screen 103 is further provided inside the washing and filtering device 1, and the drain port of the washing and filtering device 1 is located below the screen 103.

[0074] Preferably, the acidolysis device 3 comprises an acidolysis reaction tank 301 and a first waste gas absorption tank 302. The liquid inlet of the acidolysis reaction tank 301 is connected to the liquid discharge port of the activated carbon adsorption device 2 through a liquid infusion tube, and the exhaust port of the acidolysis reaction tank 301 is connected to the air inlet of the first waste gas absorption tank 302 through an air infusion tube. The acidolysis reaction tank 301 is also provided with an acid addition port 303, and the acidolysis reaction tank 301 is also provided with a first heating mechanism 304 and a first temperature detector 305. The first heating mechanism 304 is one of a heating tube, a heating plate, and a heating wire.

[0075] Preferably, the liquid discharge port of the freezing separation device 4 is also connected to the acid addition port 303 of the acidolysis reaction tank 301 through an acid liquid circulation pipeline 401 .

[0076] Preferably, the high-efficiency chemical combination barrel 6 comprises a barrel body 601, a first stirring motor 602, a first stirring shaft 603 and a first stirring blade 604. The first stirring motor 602 is arranged at the top of the barrel body 601, the upper end of the first stirring shaft 603 is connected to the first stirring motor 602, and the lower end thereof extends into the barrel body 601, and the first stirring blade 604 is arranged at the middle and lower part of the first stirring shaft 603. The first stirring blade 604 is a sheet-like structure whose thickness gradually decreases along its rotation direction and whose upper surface is an inclined surface. A second temperature detector 605 is also arranged in the barrel body 601.

[0077] Preferably, the upper annular spraying pipe 7 and the lower annular spraying pipe 8 are both fixed inside the barrel 601 by a fixing bracket 606, and are both located above the stirring blade 604, and the stirring shaft 603 passes through the ring centers of the upper annular spraying pipe 7 and the lower annular spraying pipe 8 in sequence. The upper annular spraying pipe 7 is evenly distributed along its circumference with a plurality of upper annular nozzles 701 facing vertically downward, and the lower annular spraying pipe 8 is evenly distributed along its circumference with a plurality of lower annular nozzles 801 facing vertically upward, and the number of the upper annular nozzles 701 is consistent with the number of the lower annular nozzles 801, and they correspond one to one.

[0078] Preferably, the upper ring nozzle 701 includes an upper injection hole 7011, a herringbone nozzle 7012 and an ultrasonic block 7013. The herringbone nozzle 7012 is composed of an upper through pipe, a herringbone pipe and a lower through pipe connected in series from top to bottom. The upper through pipe of the herringbone nozzle 7012 is connected to the upper annular spraying pipeline 7, the upper injection hole 7011 is provided on the inner side wall of the lower through pipe of the herringbone nozzle 7012, and the ultrasonic block 7013 is arranged on the outer side wall of the lower through pipe of the herringbone nozzle 7012. Preferably, the upper ring nozzle 701 includes a plurality of herringbone pipes, and the plurality of herringbone pipes are evenly arranged around the lower side of the upper through pipe, and the upper ends of all the herringbone pipes are simultaneously connected to the lower end of the upper through pipe, and the lower end of each herringbone pipe is connected to the lower through pipe.

[0079] Preferably, the lower annular nozzle 801 comprises a lower injection hole 8011, a vertical nozzle 8012 and a movable pipe 8013. The lower end of the vertical nozzle 8012 is connected to the lower annular spraying pipe 8, and the movable pipe 8013 is sleeved and arranged in the tube cavity of the vertical nozzle 8012 from top to bottom, and can move up and down in the tube cavity of the vertical nozzle 8012. The lower injection hole 8011 is arranged on the tube wall of the movable pipe 8013. The outer diameter of the movable pipe 8013 is smaller than the inner diameter of the vertical nozzle 8012, and an annular baffle 8014 is arranged around the outer side of the bottom end of the movable pipe 8013, and the top of the vertical nozzle 8012 is a shrinking design. The upper end of the vertical nozzle 8012 is flush with the lower end of the lower through pipe of the herringbone nozzle 7012, and the top of the movable pipe 8013 is provided with a herringbone limiting protrusion 8015 matching the herringbone nozzle 7012. Preferably, when the movable tube 8013 is fully extended from the vertical nozzle 8012, the upper injection holes 7011 and the lower injection holes 8011 are opposite to each other one by one, and in the vertical direction, the distance between the upper injection holes 7011 and the lower injection holes 8011 at the same horizontal height gradually increases from top to bottom.

[0080] Preferably, the system further comprises a purification and refinement unit, the purification and refinement unit comprising a mixing barrel 11 and a cylindrical screen 12, the mixing barrel 11 comprising a cylindrical barrel body and a conical barrel bottom arranged at the lower end of the barrel body. The cylindrical screen 12 is fixed inside the barrel body of the mixing barrel 11 by a fixing rod 1201, and sieve holes 1202 are provided on the top wall, bottom wall and side wall of the cylindrical screen 12. A second stirring motor 1101 is provided on the top of the mixing barrel 11, the upper end of the second stirring shaft 1102 is connected to the second stirring motor 1101, and the lower end thereof passes through the cylindrical screen 12 downward and then extends to the inner cavity of the mixing barrel 11 located below the cylindrical screen 12. Second stirring blades 1103 are provided on the second stirring shaft 1102 located inside the cylindrical screen 12 and below the cylindrical screen 12. A liquid injection pipe 1104 and a feed pipe 1105 are also provided on the top of the mixing barrel 11, and the lower end of the feed pipe 1105 extends downward to the inside of the cylindrical screen 12, and the upper end of the feed pipe 1105 is connected to the salt outlet of the high-efficiency combination barrel 6 through the coarse material conveying device 13.

[0081] Preferably, the system further comprises an evaporation concentration device 14 and a second waste gas absorption tank 15, wherein the liquid inlet of the evaporation concentration device 14 is connected to the liquid discharge port of the high-efficiency combination barrel 6 via a liquid infusion pipe, the gas inlet of the second waste gas absorption tank 15 is connected to the gas outlet of the high-efficiency combination barrel 6 via a gas infusion pipe, and the liquid discharge port of the second waste gas absorption tank 15 is connected to the liquid inlet of the evaporation concentration device 14 via a liquid infusion pipe. The second waste gas absorption tank 15 is provided with an alkali solution inlet 1501.

[0082] Preferably, a third temperature detector 1106 is further provided in the barrel body of the mixing barrel 11. An ultrasonic generating plate 1107 and a second heating mechanism 1108 are also provided on the conical barrel bottom of the mixing barrel 11, and the second heating mechanism 1108 is one of a heating tube, a heating plate, and a heating wire.

[0083] Preferably, the pore size of the sieve hole 1202 is 10-200 nm, preferably 30-180 nm, and more preferably 50-150 nm.

[0084] Preferably, the second stirring blade 1103 is an arc-shaped stirring blade, and a serrated protrusion is also provided on the blade edge in the rotation direction thereof.

[0085] Example 1

[0086] like Figure 1-7As shown, a treatment system for industrial mixed waste salt containing sulfate, the system includes an adsorption and impurity removal unit, an acid dechlorination unit and a convection chemical combination unit. The adsorption and impurity removal unit includes a washing and filtering device 1 and an activated carbon adsorption device 2 which are arranged in series. The acid dechlorination unit includes an acidolysis device 3, a freezing separation device 4 and a dissolution tank 5. The convection chemical combination unit includes a high-efficiency chemical combination barrel 6 and an upper annular spraying pipe 7 and a lower annular spraying pipe 8 which are arranged in parallel in the high-efficiency chemical combination barrel 6. An upper annular spraying pipe 7 is provided on the upper annular spraying pipe 7, and a lower annular spraying pipe 8 is provided on the lower annular spraying pipe 8. The upper spray hole 7011 of the upper annular nozzle 701 is arranged opposite to the lower spray hole 8011 of the lower annular nozzle 801. The discharge end of the mixed waste salt conveying device 101 is connected to the feed port of the washing and filtering device 1, the discharge port of the washing and filtering device 1 is connected to the liquid inlet of the activated carbon adsorption device 2 through an infusion pipe, the discharge port of the activated carbon adsorption device 2 is connected to the liquid inlet of the acidolysis device 3 through an infusion pipe, the discharge port of the acidolysis device 3 is connected to the liquid inlet of the freezing separation device 4 through an infusion pipe, the discharge port of the freezing separation device 4 is connected to the feed port of the dissolution tank 5 through the infusion pipe, the discharge port of the dissolution tank 5 is connected to the liquid inlet of the lower annular spraying pipe 8 through the infusion pipe, and the liquid inlet of the upper annular spraying pipe 7 is connected to the barium sulfide solution conveying pipe 9.

[0087] Example 2

[0088] Example 1 is repeated, except that the system also includes a pretreatment unit, which is a pyrolysis furnace or an incinerator 10, and the discharge end of the mixed waste salt conveying device 101 is connected to the feed port of the pyrolysis furnace or the incinerator 10, and the discharge port of the pyrolysis furnace or the incinerator 10 is connected to the feed port of the washing and filtering device 1 through a conveying pipe.

[0089] Example 3

[0090] Example 2 is repeated, except that the washing and filtering device 1 is further provided with a water inlet connected to the water inlet pipe 102. A screen 103 is further provided inside the washing and filtering device 1, and the drain port of the washing and filtering device 1 is located below the screen 103.

[0091] Example 4

[0092] Example 3 is repeated, except that the acidolysis device 3 includes an acidolysis reaction tank 301 and a first waste gas absorption tank 302. The liquid inlet of the acidolysis reaction tank 301 is connected to the liquid discharge port of the activated carbon adsorption device 2 through a liquid infusion tube, and the exhaust port of the acidolysis reaction tank 301 is connected to the air inlet of the first waste gas absorption tank 302 through a gas infusion tube. The acidolysis reaction tank 301 is also provided with an acid addition port 303, and the acidolysis reaction tank 301 is also provided with a first heating mechanism 304 and a first temperature detector 305. The first heating mechanism 304 is an electric heating plate.

[0093] Example 5

[0094] Example 4 is repeated, except that the liquid discharge port of the freezing separation device 4 is further connected to the acid addition port 303 of the acidolysis reaction tank 301 through the acid liquid circulation pipeline 401.

[0095] Example 6

[0096] Example 5 is repeated, except that the high-efficiency chemical combination barrel 6 includes a barrel body 601, a first stirring motor 602, a first stirring shaft 603 and a first stirring blade 604. The first stirring motor 602 is arranged on the top of the barrel body 601, the upper end of the first stirring shaft 603 is connected to the first stirring motor 602, and the lower end thereof extends into the barrel body 601, and the first stirring blade 604 is arranged at the middle and lower part of the first stirring shaft 603. The first stirring blade 604 is a sheet-like structure whose thickness gradually decreases along its rotation direction and whose upper surface is an inclined surface. A second temperature detector 605 is also arranged in the barrel body 601.

[0097] Example 7

[0098] Example 6 is repeated, except that the upper annular spraying pipe 7 and the lower annular spraying pipe 8 are both fixed inside the barrel 601 by a fixing bracket 606, and are both located above the stirring blade 604, and the stirring shaft 603 passes through the ring center of the upper annular spraying pipe 7 and the lower annular spraying pipe 8 in sequence. The upper annular spraying pipe 7 is evenly distributed along its circumference with a plurality of upper annular nozzles 701 facing vertically downward, and the lower annular spraying pipe 8 is evenly distributed along its circumference with a plurality of lower annular nozzles 801 facing vertically upward, and the number of the upper annular nozzles 701 is consistent with the number of the lower annular nozzles 801, and corresponds one to one.

[0099] Example 8

[0100] Repeat Example 7, except that the upper ring nozzle 701 includes an upper injection hole 7011, a herringbone nozzle 7012 and an ultrasonic block 7013. The herringbone nozzle 7012 is composed of an upper through pipe, a herringbone pipe and a lower through pipe connected in series from top to bottom. The upper through pipe of the herringbone nozzle 7012 is connected to the upper annular spraying pipeline 7, the upper injection hole 7011 is opened on the inner side wall of the lower through pipe of the herringbone nozzle 7012, and the ultrasonic block 7013 is arranged on the outer side wall of the lower through pipe of the herringbone nozzle 7012. The upper ring nozzle 701 includes a plurality of herringbone pipes, and the plurality of herringbone pipes are evenly arranged around the lower side of the upper through pipe, and the upper ends of all the herringbone pipes are simultaneously connected to the lower end of the upper through pipe, and the lower end of each herringbone pipe is connected to the lower through pipe.

[0101] Example 9

[0102] Repeat Example 8, except that the lower annular nozzle 801 includes a lower injection hole 8011, a vertical nozzle 8012 and a movable pipe 8013. The lower end of the vertical nozzle 8012 is connected to the lower annular spraying pipe 8, and the movable pipe 8013 is sleeved and arranged in the tube cavity of the vertical nozzle 8012 from top to bottom, and can move up and down in the tube cavity of the vertical nozzle 8012. The lower injection hole 8011 is arranged on the tube wall of the movable pipe 8013. The outer diameter of the movable pipe 8013 is smaller than the inner diameter of the vertical nozzle 8012, and an annular baffle 8014 is arranged around the outer side of the bottom end of the movable pipe 8013, and the top of the vertical nozzle 8012 is a shrinking design. The upper end of the vertical nozzle 8012 is flush with the lower end of the lower through pipe of the herringbone nozzle 7012, and the top of the movable pipe 8013 is provided with a herringbone limiting protrusion 8015 matching the herringbone nozzle 7012. When the movable tube 8013 is fully extended out of the vertical nozzle 8012, the upper injection holes 7011 and the lower injection holes 8011 are opposite to each other one by one, and in the vertical direction, the distance between the upper injection holes 7011 and the lower injection holes 8011 located at the same level gradually increases from top to bottom.

[0103] Example 10

[0104] Example 9 is repeated, except that the system also includes a purification and refinement unit, which includes a mixing barrel 11 and a cylindrical screen 12. The mixing barrel 11 includes a cylindrical barrel body and a conical barrel bottom arranged at the lower end of the barrel body. The cylindrical screen 12 is fixed inside the barrel body of the mixing barrel 11 by a fixing rod 1201, and sieve holes 1202 are provided on the top wall, bottom wall and side wall of the cylindrical screen 12. A second stirring motor 1101 is provided on the top of the mixing barrel 11, and the upper end of the second stirring shaft 1102 is connected to the second stirring motor 1101, and the lower end thereof penetrates downwardly through the cylindrical screen 12 and extends to the inner cavity of the mixing barrel 11 located below the cylindrical screen 12. Second stirring blades 1103 are provided on the second stirring shaft 1102 located inside the cylindrical screen 12 and below the cylindrical screen 12. A liquid injection pipe 1104 and a feed pipe 1105 are also provided on the top of the mixing barrel 11, and the lower end of the feed pipe 1105 extends downward to the inside of the cylindrical screen 12, and the upper end of the feed pipe 1105 is connected to the salt outlet of the high-efficiency combination barrel 6 through the coarse material conveying device 13.

[0105] Embodiment 11

[0106] Example 10 is repeated, except that the system further includes an evaporation concentration device 14 and a second waste gas absorption tank 15, the liquid inlet of the evaporation concentration device 14 is connected to the liquid discharge port of the high-efficiency combination barrel 6 through a liquid infusion pipe, the air inlet of the second waste gas absorption tank 15 is connected to the air outlet of the high-efficiency combination barrel 6 through a gas infusion pipe, and the liquid discharge port of the second waste gas absorption tank 15 is connected to the liquid inlet of the evaporation concentration device 14 through a liquid infusion pipe. The second waste gas absorption tank 15 is provided with an alkali solution inlet 1501.

[0107] Example 12

[0108] Example 11 is repeated, except that a third temperature detector 1106 is further provided in the barrel body of the mixing barrel 11. An ultrasonic generating plate 1107 and a second heating mechanism 1108 are also provided on the conical barrel bottom of the mixing barrel 11, and the second heating mechanism 1108 is one of a heating tube, a heating plate, and a heating wire.

[0109] Embodiment 13

[0110] Example 12 was repeated except that the pore size of the mesh 1202 was 50 nm.

[0111] Embodiment 14

[0112] Example 12 was repeated except that the pore size of the mesh 1202 was 80 nm.

[0113] Embodiment 15

[0114] Example 12 was repeated except that the pore size of the mesh 1202 was 100 nm.

[0115] Example 16

[0116] Example 15 is repeated, except that the second stirring blade 1103 is an arc-shaped stirring blade, and a serrated protrusion is also provided on the blade edge in the rotation direction.

Claims

1. A system for treating industrial mixed waste salt containing sulfate, characterized in that: The system comprises an adsorption and impurity removal unit, an acid dechlorination unit and a convection and chemical combination unit; the adsorption and impurity removal unit comprises a washing and filtering device (1) and an activated carbon adsorption device (2) which are sequentially arranged in series; the acid dechlorination unit comprises an acid decomposition device (3), a freezing separation device (4) and a dissolution tank (5); the convection and chemical combination unit comprises a high-efficiency chemical combination barrel (6) and an upper annular spraying pipe (7) and a lower annular spraying pipe (8) which are arranged in parallel in the high-efficiency chemical combination barrel (6); an upper annular spraying pipe (7) is provided on the upper annular spraying pipe (7), a lower annular spraying pipe (8) is provided on the lower annular spraying pipe (8), an upper spray hole (7011) of the upper annular nozzle (701) and a lower spray hole (8011) of the lower annular nozzle (801) are connected to each other. 11) are arranged relatively to each other; the discharge end of the mixed waste salt conveying device (101) is connected to the feed port of the washing and filtering device (1), the discharge port of the washing and filtering device (1) is connected to the liquid inlet of the activated carbon adsorption device (2) through a liquid infusion pipe, the discharge port of the activated carbon adsorption device (2) is connected to the liquid inlet of the acidolysis device (3) through a liquid infusion pipe, the discharge port of the acidolysis device (3) is connected to the liquid inlet of the freezing separation device (4) through a liquid infusion pipe, the discharge port of the freezing separation device (4) is connected to the feed port of the dissolution tank (5) through a liquid infusion pipe, the discharge port of the dissolution tank (5) is connected to the liquid inlet of the lower annular spraying pipe (8) through a liquid infusion pipe, and the liquid inlet of the upper annular spraying pipe (7) is connected to the barium sulfide solution conveying pipe (9).

2. The system for treating industrial mixed waste salt containing sulfate according to claim 1, characterized in that: The system also includes a pretreatment unit, which is a pyrolysis furnace or an incinerator (10). The discharge end of the mixed waste salt conveying device (101) is connected to the feed port of the pyrolysis furnace or the incinerator (10), and the discharge port of the pyrolysis furnace or the incinerator (10) is connected to the feed port of the washing and filtering device (1) through a conveying pipe.

3. The system for treating industrial mixed waste salt containing sulfate according to claim 1 or 2, characterized in that: The washing and filtering device (1) is also provided with a water inlet connected to the water inlet pipe (102); a screen (103) is also provided inside the washing and filtering device (1), and a liquid discharge port of the washing and filtering device (1) is located below the screen (103); and / or The acidolysis device (3) comprises an acidolysis reaction tank (301) and a first waste gas absorption tank (302); the liquid inlet of the acidolysis reaction tank (301) is connected to the liquid discharge port of the activated carbon adsorption device (2) via a liquid infusion pipe, and the exhaust port of the acidolysis reaction tank (301) is connected to the air inlet of the first waste gas absorption tank (302) via an air infusion pipe; the acidolysis reaction tank (301) is also provided with an acid addition port (303), and the acidolysis reaction tank (301) is also provided with a first heating mechanism (304) and a first temperature detector (305); the first heating mechanism (304) is one of a heating tube, a heating plate, and a heating wire; and / or The liquid discharge port of the freezing separation device (4) is also connected to the acid addition port (303) of the acidolysis reaction tank (301) through an acid liquid circulation pipeline (401).

4. The system for treating industrial mixed waste salt containing sulfate according to claim 3, characterized in that: The high-efficiency chemical combination barrel (6) comprises a barrel body (601), a first stirring motor (602), a first stirring shaft (603) and a first stirring blade (604); the first stirring motor (602) is arranged at the top of the barrel body (601), the upper end of the first stirring shaft (603) is connected to the first stirring motor (602), and the lower end thereof extends into the barrel body (601); the first stirring blade (604) is arranged at the middle and lower part of the first stirring shaft (603); the first stirring blade (604) is a sheet-like structure whose thickness gradually decreases along its rotation direction and whose upper surface is an inclined surface; a second temperature detector (605) is also arranged in the barrel body (601).

5. The system for treating industrial mixed waste salt containing sulfate according to claim 4, characterized in that: The upper annular spraying pipe (7) and the lower annular spraying pipe (8) are both fixed inside the barrel (601) by a fixing bracket (606) and are both located above the stirring blade (604). The stirring shaft (603) passes through the ring centers of the upper annular spraying pipe (7) and the lower annular spraying pipe (8) in sequence. The upper annular spraying pipe (7) is evenly distributed along its circumference with a plurality of upper annular nozzles (701) pointing vertically downward, and the lower annular spraying pipe (8) is evenly distributed along its circumference with a plurality of lower annular nozzles (801) pointing vertically upward. The number of the upper annular nozzles (701) is consistent with the number of the lower annular nozzles (801) and corresponds one to one.

6. The system for treating industrial mixed waste salt containing sulfate according to claim 5, characterized in that: The upper annular nozzle (701) comprises an upper injection hole (7011), a herringbone nozzle (7012) and an ultrasonic block (7013); the herringbone nozzle (7012) is composed of an upper through pipe, a herringbone pipe and a lower through pipe which are connected in series from top to bottom; the upper through pipe of the herringbone nozzle (7012) is connected to the upper annular spraying pipe (7), the upper injection hole (7011) is provided on the inner wall of the lower through pipe of the herringbone nozzle (7012), and the ultrasonic block (7013) is arranged on the outer wall of the lower through pipe of the herringbone nozzle (7012).

7. The system for treating industrial mixed waste salt containing sulfate according to claim 6, characterized in that: The upper ring nozzle (701) comprises a plurality of herringbone tubes, which are evenly arranged around the lower part of the upper through pipe, and the upper ends of all the herringbone tubes are simultaneously connected to the lower end of the upper through pipe, and the lower end of each herringbone tube is connected to the lower through pipe.

8. The system for treating industrial mixed waste salt containing sulfate according to claim 6 or 7, characterized in that: The lower annular nozzle (801) comprises a lower spray hole (8011), a vertical spray pipe (8012) and a movable pipe (8013); the lower end of the vertical spray pipe (8012) is connected to the lower annular spray pipe (8); the movable pipe (8013) is sleeved from top to bottom in the tube cavity of the vertical spray pipe (8012) and can move up and down in the tube cavity of the vertical spray pipe (8012); the lower spray hole (8011) is arranged on the tube wall of the movable pipe (8013); The outer diameter of the movable pipe (8013) is smaller than the inner diameter of the vertical nozzle (8012), and an annular baffle (8014) is provided around the outer side of the bottom end of the movable pipe (8013), and the top end of the vertical nozzle (8012) is designed as a constricted mouth; the upper end of the vertical nozzle (8012) is flush with the lower end of the lower through pipe of the herringbone nozzle (7012), and the top end of the movable pipe (8013) is provided with a herringbone limiting protrusion (8015) matching the herringbone nozzle (7012).

9. The system for treating industrial mixed waste salt containing sulfate according to claim 8, characterized in that: When the movable tube (8013) is fully extended from the vertical nozzle (8012), the upper injection holes (7011) and the lower injection holes (8011) are opposite to each other one by one, and in the vertical direction, the distance between the upper injection holes (7011) and the lower injection holes (8011) at the same level gradually increases from top to bottom.

10. The system for treating industrial mixed waste salt containing sulfate according to any one of claims 1-2, 4-7, and 9, characterized in that: The system also includes a purification and refinement unit, the purification and refinement unit including a mixing barrel (11) and a cylindrical screen (12), the mixing barrel (11) including a cylindrical barrel body and a conical barrel bottom arranged at the lower end of the barrel body; the cylindrical screen (12) is fixed inside the barrel body of the mixing barrel (11) through a fixing rod (1201), and screen holes (1202) are opened on the top wall, bottom wall and side wall of the cylindrical screen (12); a second stirring motor (1101) is arranged on the top of the mixing barrel (11), the upper end of the second stirring shaft (1102) is connected to the second stirring motor (1101), and the lower end thereof is connected to the second stirring motor (1101). The mixing barrel (1106) is a mixing barrel having a plurality of mixing elements, each of which is agitated by a plurality of stirring blades (1103). The mixing barrel (1106) is a mixing barrel having a plurality of mixing elements, and a plurality of mixing elements are connected to the mixing barrel (6). The mixing barrel (1106) is a mixing barrel having a plurality of mixing elements, and a plurality of mixing elements are connected to the mixing barrel (6). The mixing barrel (1106) is a mixing barrel having a plurality of mixing elements, and a plurality of mixing elements are connected to the mixing barrel (6). The mixing barrel (1106) is a mixing barrel having a plurality of mixing elements, and a plurality of mixing elements are connected to the mixing barrel (6).

11. The system for treating industrial mixed waste salt containing sulfate according to claim 10, characterized in that: The system also includes an evaporation concentration device (14) and a second waste gas absorption tank (15); the liquid inlet of the evaporation concentration device (14) is connected to the liquid discharge port of the high-efficiency combination barrel (6) through a liquid infusion pipe, the air inlet of the second waste gas absorption tank (15) is connected to the air outlet of the high-efficiency combination barrel (6) through a gas infusion pipe, and the liquid discharge port of the second waste gas absorption tank (15) is connected to the liquid inlet of the evaporation concentration device (14) through a liquid infusion pipe; and the second waste gas absorption tank (15) is provided with an alkali solution inlet (1501).

12. The system for treating industrial mixed waste salt containing sulfate according to claim 11, characterized in that: A third temperature detector (1106) is also provided inside the barrel body of the mixing barrel (11); an ultrasonic generating plate (1107) and a second heating mechanism (1108) are also provided on the conical barrel bottom of the mixing barrel (11); the second heating mechanism (1108) is one of a heating tube, a heating plate, and a heating wire.

13. The system for treating industrial mixed waste salt containing sulfate according to claim 12, characterized in that: The pore size of the sieve (1202) is 10-200 nm.

14. The system for treating industrial mixed waste salt containing sulfate according to claim 13, characterized in that: The pore size of the sieve (1202) is 30-180 nm.

15. The system for treating industrial mixed waste salt containing sulfate according to claim 14, characterized in that: The pore size of the sieve (1202) is 50-150 nm.

16. The system for treating industrial mixed waste salt containing sulfate according to claim 10, characterized in that: The second stirring blade (1103) is an arc-shaped stirring blade, and a serrated protrusion is also provided on the blade edge in the rotation direction.

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